This invention is directed to a process to prepare addition products of difunctional telechelic polyolefins containing functional groups which predominantly comprise terminal functional reactive groups by a simultaneous ring-opening olefin metathesis polymerization (ROMP) and addition reaction in the presence of cyclic olefins, difunctional acyclic olefins, and reagent (YZ) which undergoes addition to carbon-to-carbon double bonds.
Conventional ring-opening olefin metathesis polymerization (ROMP) is the catalyzed reaction of a cyclic olefin monomer to yield an unsaturated polymer as follows: ##STR1##
Procedures to prepare polymeric hydrocarbons having reactive functional endgroups have utilized cyclic olefinic compounds in conjunction with a ring opening step. Ofstead (U.S. Pat. No. 3,597,403) teaches a process for ring-opening polymerization of unsaturated alicyclic compounds (preferably unsaturated alicyclic compounds of a single unsaturated alicyclic ring containing at least four carbon atoms and not more than five carbon atoms wherein the carbon-to-carbon double bonds in the ring are not adjacent and are non-conjugated) in the presence of a catalyst system comprising an alkylaluminum halide, molecular oxygen, and a compound of tungsten or molybdenum. Streck et al. (U.S. Pat. No. 3,798,175) teaches a process for ring opening polymerization of cyclic olefins and forming terminal carbalkoxy groups by employing a catalyst system consisting essentially of (1) a tungsten or molybdenum compound, (2) an organo aluminum compound, and (3) an unsaturated carboxylic acid ester. Streck et al. (U.S. Pat. No. 3,857,825) discloses a process for production of polymeric hydrocarbons having reactive silyl end groups by a ring-opening polymerization of a cyclic olefin in the presence of a catalytic amount of a halogenated compound of a metal selected from the group consisting of niobium, tantalum, molybdenum, tungsten and rhenium and a halogen, alkoxy, carboxylate or Lewis acid.
Although the prior art teaches the preparation of unsaturated polymeric hydrocarbons having functional endgroups such as esters, amines, alcohols and other reactive groups, there has been no reported success in the preparation of addition products of difunctional telechelic polyolefins by simultaneous olefin metathesis reaction and addition reaction wherein the resulting difunctional telechelic polyolefins contain addition moieties which restrict or entirely change the olefinic characteristics of the resultant product. A potential problem of performing the olefin metathesis and addition reactions simultaneously is that the olefin reactants (especially the cyclic olefins) might rapidly undergo the addition reaction, yielding saturated molecules unable to undergo olefin metathesis. In such a case little or no polymer product would be obtained. Surprisingly, this is not a serious problem in the present invention and good yields of the partially-saturated polymer products can be obtained.
Utilizing the simultaneous ROMP and addition reaction process of the present invention, the resultant product has additional beneficial properties compared to ordinary unsaturated difunctional telechelic polyolefins such as being more oxidatively stable, resistant to attack by ozone and less susceptible to degradation due to exposure to UV light, and is suitable for further reactions. The process of the claimed invention saves time and eliminates the potential need for employing two separate reactors (for the ROMP reaction and for the addition reaction) and isolating the intermediate unsaturated polyolefin product of the ROMP reaction.